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Water chemistry and its ecological implications have been extensively investigated in temperate high‐mountain lakes because of their role as sentinels of global change. However, few studies have considered the drivers of water chemistry in tropical mountain lakes underlain by volcanic bedrock. A survey of 165 páramo lakes in the Cajas Massif of the Southern Ecuador Andes identified 4 independent chemical variation gradients, primarily characterized by divalent cations (hardness), organic carbon, silica, and iron levels. Hardness and silica factors showed contrasting relationships with parent rock type and age, vegetation, aquatic ecosystems in the watershed, and lake and watershed size. Geochemical considerations suggest that divalent cations (and related alkalinity, conductivity, and pH) mainly respond to the cumulative partial dissolution of primary aluminosilicates distributed throughout the subsurface of watersheds, and silica and monovalent cations are associated with the congruent dissolution of large amounts of secondary aluminosilicates localized in former hydrothermal or tectonic spots. Dissolved organic carbon was much higher than in temperate high‐mountain lakes, causing extra acidity in water. The smaller the lakes and their watersheds, the higher the likelihood of elevated organic carbon and metals and low hardness. The watershed wetland cover favored metal levels in the lakes but not organic carbon. Phosphorus, positively, and nitrate, negatively, weakly correlated with the metal gradient, indicating common influence by in‐lake processes. Overall, the study revealed that relatively small tropical lake districts on volcanic basins can show chemical variation equivalent to that in large mountain ranges with a combination of plutonic, metamorphic, and carbonate rock areas.

The number, size, and shape of lakes are key determinants of the ecological functionality of a lake district. The lake area scaling relationships with lake number and volume enable upscaling biogeochemical processes and spatially considering organisms' metapopulation dynamics. These relationships vary regionally depending on the geomorphological context, particularly in the range of lake area <1 km2and mountainous regions. The Cajas Massif (Southern Ecuador) holds a tropical mountain lake district with 5955 water bodies. The number of lakes deviates from a power law relationship with the lake area at both ends of the size range; similarly to the distributions found in temperate mountain ranges. The deviation of each distribution tail does not respond to the same cause. The marked relief limits the size of the largest lakes at high altitudes, whereas ponds are prompt to a complete infilling. A bathymetry survey of 202 lakes, selected across the full‐size range, revealed a volume‐area scaling coefficient larger than those found for other lake areas of glacial origin but softer relief. Water renewal time is not consistently proportional to the lake area due to the volume‐area variation in midsize lakes. The 85% of the water surface is in lakes >104m2and 50% of the water resources are held in a few ones (∼10) deeper than 18 m. Therefore, midlakes and large lakes are by far more biogeochemically relevant than ponds and shallow lakes in this tropical mountain lake district. The tropical high‐mountain lakes show power‐law lake‐size distributions truncated at both ends similar to those found in temperate rangesThe marked relief limits the size of the largest lakes at high altitudes, whereas ponds are particularly prompt to a complete infillingLake volume scales to lake area according to a larger coefficient than found in other lake areas of glacial origin but gentle relief